Ruthenium oxide gas absorbent liquid, analysis method for ruthenium oxide, trap device, and quantitative analyzer

Abstract

A ruthenium oxide gas absorbent liquid includes an organic alkali solution containing a ligand and/or an onium salt composed of an onium ion and an anion, at least part of which is a hydroxide ion, wherein the hydroxide ion has a concentration ranging from more than 1×10−7 mol/L to 6 mol/L or less.

1 . A ruthenium oxide gas absorbent liquid comprising an organic alkali solution containing an onium salt composed of an onium ion and an anion, at least part of which is a hydroxide ion, wherein the hydroxide ion has a concentration ranging from more than 1×10 −7  mol/L to 6 mol/L or less. 
     
     
         2 . The ruthenium oxide gas absorbent liquid according to  claim 1 , wherein the onium ion is a quaternary onium ion represented by formula (1) or a tertiary onium ion represented by formula (2): 
       
         
           
           
               
               
           
         
         wherein in formula (1), A +  is an ammonium ion or a phosphonium ion, and R 1 , R 2 , R 3 , and R 4  are each a C 1-25  alkyl group, an allyl group, a C 1-25  alkyl-containing aralkyl group, or an aryl group, provided that when R 1 , R 2 , R 3 , or R 4  is an alkyl group or an allyl group, at least one hydrogen of R 1 , R 2 , R 3 , or R 4  is optionally substituted by a hydroxyl group, a carboxyl group, a cyano group, an amino group, a thiol group, a halogen group, or a sulfonic acid group and at least one hydrogen of a ring of the aryl group or an aryl group in the aralkyl group is optionally substituted by a fluorine atom, a chlorine atom, a C 1-10  alkyl group, a C 2-10  alkenyl group, a C 1-9  alkoxy group, or a C 2-9  alkenyloxy group, where at least one hydrogen is optionally substituted by a fluorine atom or a chlorine atom; and in formula (2), A +  is a sulfonium ion, and R 1 , R 2 , and R 3  are each a C 1-25  alkyl group, an allyl group, a C 1-25  alkyl-containing aralkyl group, or an aryl group, and at least one hydrogen of a ring of the aryl group or an aryl group in the aralkyl group is optionally substituted by a fluorine atom, a chlorine atom, a C 1-10  alkyl group, a C 2-10  alkenyl group, a C 1-9  alkoxy group, or a C 2-9  alkenyloxy group, where at least one hydrogen is optionally substituted by a fluorine atom or a chlorine atom. 
       
     
     
         3 . The ruthenium oxide gas absorbent liquid according to  claim 2 , wherein the onium ion is represented by formula (1), and is a quaternary onium ion where R 1 , R 2 , R 3 , and R 4  are each a C 1-4  alkyl group. 
     
     
         4 . The ruthenium oxide gas absorbent liquid according to  claim 2 , wherein the quaternary onium ion is an ammonium ion. 
     
     
         5 . The ruthenium oxide gas absorbent liquid according to  claim 4 , wherein the ammonium ion is a tetraalkylammonium ion. 
     
     
         6 . The ruthenium oxide gas absorbent liquid according to  claim 5 , wherein the tetraalkylammonium ion is at least one tetraalkylammonium ion selected from a tetramethylammonium ion, a tetraethylammonium ion, a tetrapropylammonium ion, or a tetrabutylammonium ion. 
     
     
         7 . The ruthenium oxide gas absorbent liquid according to  claim 1 , further comprising, as a ruthenium oxide gas generation inhibitor, an onium salt composed of an onium ion and another anion other than a hydroxide. 
     
     
         8 . The ruthenium oxide gas absorbent liquid according to  claim 7 , wherein the other anion is at least one ion selected from a fluoride ion, a chloride ion, an iodide ion, a nitrate ion, a phosphate ion, a sulfate ion, a hydrogen sulfate ion, a methane sulfate ion, a perchlorate ion, a chlorate ion, a chlorite ion, a hypochlorite ion, an orthoperiodate ion, a metaperiodate ion, an iodate ion, an iodite ion, a hypoiodite ion, an acetate ion, a carbonate ion, a bicarbonate ion, a fluoroborate ion, or a trifluoroacetate ion. 
     
     
         9 . The ruthenium oxide gas absorbent liquid according to  claim 1 , further comprising, as a ruthenium oxide gas generation inhibitor, a ligand coordinated to ruthenium. 
     
     
         10 . The ruthenium oxide gas absorbent liquid according to  claim 9 , wherein the ligand coordinated to ruthenium is oxalic acid, dimethyl oxalate, 1,2,3,4,5,6-cyclohexanecarboxylic acid, succinic acid, acetic acid, butane-1,2,3,4-tetracarboxylic acid, dimethylmalonic acid, glutaric acid, di-glycolic acid, citric acid, malonic acid, 1,3-adamantane dicarboxylic acid, or 2,2-bis(hydroxymethyl)propionic acid. 
     
     
         11 . The ruthenium oxide gas absorbent liquid according to  claim 1 , wherein the onium ion has a concentration of from 1×10 −7  mol/L to 8 mol/L. 
     
     
         12 . The ruthenium oxide gas absorbent liquid according to  claim 1 , further comprising water or an organic solvent. 
     
     
         13 . The ruthenium oxide gas absorbent liquid according to  claim 12 , wherein the organic solvent has a relative permittivity of 45 or less. 
     
     
         14 . The ruthenium oxide gas absorbent liquid according to  claim 12 , wherein the organic solvent is at least one compound selected from the group consisting of sulfolanes, alkylnitriles, halogenated alkanes, ethers, esters, aldehydes, ketones, and alcohols. 
     
     
         15 . The ruthenium oxide gas absorbent liquid according to  claim 12 , wherein the organic solvent in a treatment liquid has a concentration of 0.1 mass % or more. 
     
     
         16 . An analysis method for ruthenium oxide in a process gas, the method comprising: bringing a ruthenium oxide gas-containing process gas into contact with the ruthenium oxide gas absorbent liquid according to  claim 1  to recover the ruthenium oxide gas from the process gas; and then analyzing an amount of ruthenium oxide in the ruthenium oxide gas absorbent liquid. 
     
     
         17 . The analysis method according to  claim 16 , wherein the process gas is derived from a semiconductor-use chemical liquid used for processing a ruthenium metal-containing semiconductor material. 
     
     
         18 . A trap device including a trap unit disposed in an exhaust path during processing a ruthenium metal-containing semiconductor device and configured to recover a ruthenium oxide component in an exhaust gas,
 the trap unit including: a container filled with the ruthenium oxide gas absorbent liquid according to  claim 1 ; a supply unit; and a drainage pipe for discharging the ruthenium oxide gas absorbent liquid after absorption.   
     
     
         19 . A ruthenium oxide gas quantitative analyzer including:
 a trap device including a trap unit disposed in an exhaust path during processing a ruthenium metal-containing semiconductor device and configured to recover a ruthenium oxide component in an exhaust gas,   the trap unit including: a container filled with the ruthenium oxide gas absorbent liquid according to  claim 1 , a supply unit, and a drainage pipe for discharging the ruthenium oxide gas absorbent liquid after absorption; and an analysis device for quantifying the ruthenium oxide component in the absorbent liquid sampled from the trap device.   
     
     
         20 . The quantitative analyzer according to  claim 19 , wherein the analysis device is ICP emission spectrometry, ICP mass spectrometry, or ultraviolet-visible spectroscopy (UV-VIS).